Heat-treated active carbons for use in denitration, processes for producing same, denitration method using same, and denitration system using same

ABSTRACT

This invention relates to a technique for removing nitrogen oxides (NO x ) present in exhaust gases discharged from boilers and the like. When the temperature of the exhaust gas is 100° C. or below, a heat-treated active carbon produced by heat-treating a raw active carbon at 600 to 1,200° C. in a non-oxidizing atmosphere so as to remove oxygen-containing functional groups present at the surfaces thereof and thereby reduce the atomic surface oxygen/surface carbon ratio to 0.05 or less is preferably used. When the temperature of the exhaust gas exceeds 100° C., a heat-treated active carbon produced by heat-treating a raw active carbon at 600 to 1,200° C. in a non-oxidizing atmosphere and activating the surfaces thereof with sulfuric acid or nitric acid to impart oxidizing oxygen-containing functional groups thereto is preferably used.

TECHNICAL FIELD

This invention relates to the removal of nitrogen oxides present incombustion exhaust gases discharged from boilers, engines, turbines andthe like, and more particularly to an exhaust gas denitration techniquein which cold to hot nitrogen oxides can be efficiently reduced andthereby decomposed to nitrogen and water.

This invention is especially suitable for the denitration of coldexhaust gases discharged from the outlets of existing exhaust gasdenitration apparatus, boilers and the like.

Moreover, this invention also relates to the removal of nitrogen oxidespresent in ventilation gases produced in road tunnels, undergroundparking spaces, street crossings and the like, and more particularly toa low-temperature denitration technique in which nitrogen oxides havinga lower concentration (typically about 15 ppm or less) and a lowtemperature (typically ordinary temperature to about 50° C.) as comparedwith exhaust gases from boilers and the like can be efficiently reducedand thereby decomposed to nitrogen and water.

Furthermore, this invention also relates to denitration systems using aheat-treated active carbon for the removal of nitrogen oxides (NO_(x))present in exhaust gases discharged from boilers, gas turbines, enginesand combustion furnaces for burning various types of fuel. The presentinvention can be suitably used for the removal of nitrogen oxidespresent in tunnels and for the removal of nitrogen oxides present inexhaust gases from nitric acid production plants.

BACKGROUND ART

For the denitration of exhaust gases from stationary nitrogenoxide-producing sources such as boilers, a method for reducing nitrogenoxides selectively by using vanadium oxide as a catalyst and ammonia asa reducing agent (i.e., the SCR method) has conventionally been knownand is widely employed for practical purposes (“Techniques andRegulations for the Prevention of Environmental Pollution”, Volume onthe Atmosphere, p. 130, Maruzen Co., Ltd.). However, in this methodusing the vanadium oxide catalyst, the temperature of exhaust gas needsto be raised to 300° C. or above in order to achieve a practicallysufficient degree of denitration. Consequently, it is necessary toinstall a denitrator containing a catalyst bed in the high-temperaturesection of the boiler (e.g., just behind the outlet of the boiler or inthe heat transfer section of the boiler), or reheat cold exhaust gas andthereby raise its temperature. However, these techniques involve thefollowing problems.

When the denitrator is installed in the high-temperature section of theboiler, various problems arise in that the overall equipment becomescomplicated, the use of a heat-resisting material causes an increase inequipment cost, and workability for replacement of the catalyst bed isreduced. When cold exhaust gas is reheated, an additional heater isrequired, resulting in an increase in equipment cost.

Accordingly, a first object of the present invention is to provide atechnique by which the denitration of exhaust gases from stationarynitrogen oxide-producing sources such as boilers can be performed at lowtemperatures ranging from ordinary temperature (about 5 to 20° C.) toabout 150° C.

On the other hand, exhaust gases from road tunnels and the like arecharacterized in that they have a much lower NO concentration of about10 ppm or less as compared with the concentration of nitrogen oxides inexhaust gases from boilers and the like, their temperature is in thevicinity of ordinary temperature, and they are produced in enormousvolumes. Consequently, in order to remove denitrate gases from roadtunnels and the like according to the conventional SCR method, thetemperature of the gases must be raised to 300° C. or above. Thisrequires a huge amount of thermal energy and is unprofitable from aneconomical point of view.

In Japanese Patent Publication No. 41142/'95, Japanese PatentProvisional Publication No. 47227/'95 and the like, there has beenproposed a process in which low-concentration NO at ordinary temperatureis oxidized to NO₂ with ozone or the like, the resulting NO₂ is adsorbedto an adsorbent, and the highly concentrated NO₂ is decomposed bytreatment with a reducing gas such as ammonia. However, in this processinvolving an adsorption step, not only the equipment is increased insize and becomes complicated, but also the use of ozone poses a newsafety problem. This, it is difficult to put this process to practicaluse.

Accordingly, a second object of the present invention is provide atechnique by which NO present in exhaust gases from road tunnels and thelike and hence having a low concentration and a temperature in thevicinity of ordinary temperature can be directly reacted catalyticallywith ammonia and thereby decomposed to nitrogen and water.

Now, an example of exhaust gas treatment by means of a conventionalexhaust gas treating system is explained with reference to FIG. 7.

In FIG. 7, reference numeral 41 designates a boiler; 42, a denitrator;43, an air preheater; 44, a dust collector; 45, a gas-gas heater; 46, adesulfurizer; and 47, a stack.

As shown in FIG. 7, a denitrator 42 using a catalyst is installed at theoutlet of a boiler 41 or the like in order to remove nitrogen oxides(NO_(x)) present in the exhaust gas, and an air preheater 43 isinstalled at the outlet of denitrator 42 in order to lower thetemperature of the exhaust gas to about 130° C.

The exhaust gas having passed through the aforesaid air preheater 43 isdedusted in a dust collector 44, passed through a gas-gas heater 45 andthen introduced into a desulfurizer 46 where sulfur oxides (SO_(x)) areremoved therefrom. Thereafter, the exhaust gas is discharged into theatmosphere through a stack 47.

As described above, in the current practical process for the removal ofnitrogen oxides present in exhaust gas from boilers, there is used adenitrator 42 based on the selective catalytic reduction (SCR) method inwhich nitrogen oxides are decomposed to nitrogen and water vapor byusing a catalyst comprising V₂O₅ supported on TiO₂ and a reducing agentcomprising NH₃. However, this process involves the following problems.

First, a reaction temperature of 300 to 400° C. is required because ofthe performance of the catalyst. Secondly, NH₃ is required for use asreducing agent. Thirdly, since the current leak level of NO_(x) is from5 to 40 ppm, an excess of NH₃ needs to be injected for the purpose ofreducing the leak level of NO_(x) to zero.

Moreover, recent environmental standards demand that the concentrationof nitrogen oxides (NO_(x)) in exhaust gases should be reduced to alevel of 1 ppm or less which is commonly known as a high-degreedenitration level. In the aforesaid conventional denitration treatmentbased on the selective catalytic reduction (SCR) method, a markedincrease in removal cost due to an increased size of equipment and thelike is unavoidable, even though the conditions are optimized. On theother hand, it is desired from the viewpoint of environmental problemsto improve the efficiency of removal of nitrogen oxides.

Accordingly, in view of the above-described problems, a third object ofthe present invention is to provide a denitration system which canachieve an improvement in the efficiency of removal of nitrogen oxidespresent in exhaust gases as compared with the prior art.

DISCLOSURE OF THE INVENTION

The present inventors have carried out investigations with a view toaccomplishing the above-described first and second objects, and have nowfound that, when an active carbon having a large specific surface areaand high porosity (in particular, one obtained by heat-treating activecarbon fibers or a granular active carbon having a large number of finemicropores with a size of 20 Å or less under specific conditions) isused as a catalyst for the denitration reaction of exhaust gas, a highdegree of denitration can be achieved even at low temperatures of 150°C. or below. Moreover, they have also found that a high degree ofdenitration can be achieved even when exhaust gas having a low NOconcentration is treated in the vicinity of ordinary temperature.

That is, the present invention provides the following techniquesconcerning the denitration of exhaust gas. Specifically, the presentinvention provides a process for producing an active carbon for use inthe denitration of exhaust gas which comprises heat-treating a rawactive carbon at 600 to 1,200° C. in a non-oxidizing atmosphere so as toremove oxygen-containing functional groups present at the surfacesthereof and thereby reduce the atomic surface oxygen/surface carbonratio to 0.05 or less.

The present invention also provides a process for producing an activecarbon for use in denitration which comprises heat-treating a raw activecarbon at 600 to 1,200° C. in a non-oxidizing atmosphere and activatingthe surfaces thereof with sulfuric acid or nitric acid to impartoxidizing oxygen-containing functional groups thereto.

The present invention also provides a denitration method which comprisesbringing exhaust gas containing nitrogen oxides and not more than 80% ofwater as water vapor, and NH₃ gas having the same concentration as thenitrogen oxides into contact with an active carbon for use in thedenitration of exhaust gas that is produced by any of theabove-described processes, at a temperature ranging from ordinarytemperature to 150° C., in order to reduce the nitrogen oxidesselectively and thereby decompose them to nitrogen and water.

The present invention also provides the denitration method wherein ahigher degree of denitration of nitrogen oxides having a temperature of20 to 150° C. and a concentration of 5 to 400 ppm is performed at theoutlet of an exhaust gas treating apparatus or the outlet of a boiler.

In order to accomplish the above-described third object, a firstdenitration system using active carbon in accordance with the presentinvention comprises a first packed reactor which is packed with aheat-treated active carbon produced by heat-treating a raw active carbonat a temperature in the range of 600 to 1,000° C., and a second packedreactor which is located downstream thereof and packed with theheat-treated active carbon, whereby exhaust gas and ammonia (NH₃) areintroduced into the first packed reactor so as to bring nitrogen oxides(NO_(x)) present in the exhaust gas into contact with the ammonia andremove the nitrogen oxides by the continuous selective reduction of themto nitrogen (N₂), and any excess ammonia is recovered by adsorption inthe second packed reactor.

In the aforesaid denitration system, a gas to be treated can bealternately introduced into the first packed reactor and the secondpacked reactor so as to perform denitration and ammonia adsorptionrepeatedly.

In order to accomplish the above-described third object, a seconddenitration system using active carbon in accordance with the presentinvention comprises a denitrator packed with a heat-treated activecarbon which is produced by heat-treating a raw active carbon at atemperature in the range of 600 to 1,000° C., and first and secondammonia adsorbers located before and behind the denitrator,respectively, whereby exhaust gas containing nitrogen oxides isalternately introduced through any one of the first and second ammoniaadsorbers, ammonia (NH₃) is introduced at a position between the firstor second ammonia adsorber and the denitrator, nitrogen oxides (NO_(x))present in the exhaust gas are brought into contact with theheat-treated active carbon placed in the denitrator and removed by thecontinuous selective reduction of them to nitrogen (N₂), and any excessammonia is recovered by adsorption in the adsorber located downstream ofthe denitrator.

In the aforesaid denitration systems, the raw active carbon may compriseraw active carbon fibers or a raw granular active carbon. The raw activecarbon fibers preferably comprise carbon fibers derived frompolyacrylonitrile or pitch.

Moreover, in the aforesaid denitration systems, there may be used anactive carbon produced by subjecting the raw active carbon to a chemicaltreatment such as sulfuric acid treatment or metal carrying treatment,in place of the heat treatment.

The heat-treated active carbon of the present invention is highlyeffective as a catalyst for the denitration of exhaust gas. Morespecifically, when the heat-treated active carbon of the presentinvention is used for purposes of denitration, exhaust gases containingnitrogen oxides at low to high concentrations (about 20 to 500 ppm) canbe denitrated at a low temperature ranging from ordinary temperature toabout 150° C. and with a high degree of denitration of about 40 to 80%.

Especially when active carbon fibers derived from pitch are used,excellent denitration performance can be achieved even under a highpartial pressure of water vapor.

Moreover, when the heat-treated active carbon of the present inventionis used, gases containing nitrogen oxides at a low concentration of 15ppm or less can be denitrated at a low temperature ranging from ordinarytemperature to about 50° C. and with a high degree of denitration ofabout 40 to 80%, without oxidizing NO to NO₂ by means of ozone, electronrays or the like, or without concentrating nitrogen oxides by means ofan adsorbent. Especially when active carbon fibers derived from pitchare used, excellent denitration performance can be achieved even under ahigh partial pressure of water vapor.

In the denitration systems of the present invention wherein thetreatment of gases containing nitrogen oxides is performed by using anactive carbon heat-treated under specific conditions as an ammoniaadsorbent, low-concentration nitrogen oxides (NO_(x)) can be treatedand, therefore, a higher degree of denitration can be achieved.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic diagram showing the denitration reaction mechanismat the surfaces of an active carbon modified by the process of thepresent invention;

FIG. 2 is a schematic illustration of a first embodiment of thedenitration system in accordance with the present invention;

FIG. 3 is a schematic illustration of a second embodiment of thedenitration system in accordance with the present invention;

FIG. 4 is a schematic illustration of a third embodiment of thedenitration system in accordance with the present invention;

FIG. 5 is a schematic illustration of the third embodiment of thedenitration system in accordance with the present invention;

FIG. 6 is a schematic illustration of the third embodiment of thedenitration system in accordance with the present invention; and

FIG. 7 is a schematic illustration of a conventional denitration system.

BEST MODE FOR CARRYING OUT THE INVENTION

In this specification, all percentages are by volume unless otherwisestated. The term “non-oxidizing atmosphere” comprehends both inert gasatmospheres and reducing atmospheres. The term “ordinary temperature”means temperatures in the range of about 5 to 40° C.

The raw active carbon fibers which can be used in the present inventionto produce a heat-treated active carbon for use in denitration includevarious types of active carbon fibers such as those derived from pitch,PAN, phenol and cellulose. Among them, active carbon fibers derived frompitch have low nitrogen and oxygen contents and enhance the effect ofremoving oxygen-containing functional groups present at the surfacesthereof by a heat treatment which will be described later. Accordingly,they exhibit high nitrogen oxide-removing activity even under a highpartial pressure of water vapor. Thus, it is preferable to use activecarbon fibers derived from pitch. Although no particular limitation isplaced on the properties of the raw active carbon fibers, they usuallyhave a pore diameter of about 10 to 30 Å, a pore volume of about 0.3 to1.2 ml/g, and a specific surface area of about 500 to 2,000 m²/g.

In the present invention, a heat-treated active carbon which has highcatalytic activity for denitration and minimizes the influence ofmoisture in exhaust gas (hereinafter also referred to as heat-treatedactive carbon A) can be obtained by heat-treating the raw active carbonat 600 to 1,200° C. in a non-oxidizing atmosphere such as nitrogen gas,argon gas or helium gas to remove oxygen-containing functional groups(such as COOH and COH) present at the surfaces of the raw active carbonand thereby reduce the atomic oxygen/carbon ratio of the surfaces to0.05 or less.

Alternatively, a heat-treated active carbon having high catalyticactivity for denitration can also be obtained by heat-treating the rawactive carbon at 600 to 1,200° C. in a non-oxidizing atmosphere such asnitrogen gas, argon gas or helium gas, and then activating the surfacesthereof with sulfuric acid or nitric acid to impart thereto oxidizingoxygen-containing functional groups such as C═O and C₂O. In this case,the activation of the active carbon with sulfuric acid or nitric acidcan be performed by adding sulfuric acid (about 98%) or nitric acid(about 60%) to the raw active carbon in an amount equal to three to fivetimes the weight of the raw active carbon, soaking it fully, and heatingit at about 350 to 500° C. until the sulfuric acid or nitric acid isevaporated completely. In this case, there can be obtained aheat-treated active carbon for use in denitration which exhibits veryhigh denitrating activity even at low temperatures of 150° C. or belowand minimizes the influence of moisture in exhaust gas (hereinafter alsoreferred to as heat-treated active carbon B).

When the denitration of exhaust gas is performed according to the methodof the present invention, exhaust gas containing nitrogen oxides at alow to high concentration (about 500 ppm or less), 3% or more of oxygen,and 0 to 80% of moisture as water vapor is brought into contact with NH₃gas having the same concentration (or equivalent amount) as the nitrogenoxides, in the presence of the aforesaid heat-treated active carbon, ata temperature ranging from ordinary temperature (about 5 to 20° C.) toabout 150° C. (more preferably in the range of about 100 to 150° C.).Thus, the nitrogen oxides are selectively reduced and thereby decomposedto nitrogen and water.

Generally, when the temperature of the exhaust gas is relatively low(i.e., 100° C. or below), it is preferable to use the aforesaidheat-treated active carbon A, and when the temperature of the exhaustgas is relatively high (i.e., 100° C. or above), it is preferable to usethe aforesaid heat-treated active carbon B. Especially when heat-treatedactive carbon B is used, denitration can be performed even for exhaustgas having a moisture content of greater than 80%.

In the present invention, while the exhaust gas comes into contact withthe heat-treated active carbon or passes through the heat-treated activecarbon, nitrogen oxides (NO_(x)) present therein react with ammonia(NH₃) used as a reducing agent, as represented by the followingequations, and thereby decomposed to harmless nitrogen (N₂) and watervapor (H₂O).

4NO+4NH₃+O₂→4N₂+6H₂O  (1)

6NO₂+8NH₃→7N₂+12H₂O  (2)

The reaction mechanism (at temperatures higher than 100° C.) at thesurfaces of the heat-treated active carbon, which is represented byequation (1), is shown in FIG. 1.

First of all, ammonia is adsorbed to oxidizing oxygen-containingfunctional groups present at the surfaces of the heat-treated activecarbon, so that active species such as OH (ad.) and NH₂ (ad.) areformed. Then, NH₂ (ad.) reacts with NO and thereby reduced to N₂ andH₂O. After N₂ and H₂O are eliminated, the remaining —OH groups areoxidized by oxygen to regenerate oxidizing oxygen-containing functionalgroups.

The reason why these reactions proceed even at ordinary temperature isthat the heat-treated active carbon has micropores with a size of 20 Åor less, and the reactants condense in the micropores and createhigh-pressure reactions in microscopic regions.

Usually, the above-described reactions are markedly inhibited bymoisture present in the exhaust gas. This is due to the competitiveadsorption of water and O₂ or NH₃. In the present invention, however,the raw active carbon is heat-treated in a non-oxidizing atmosphere toremove hydrophilic oxygen-containing groups and thereby minimize theinfluence of moisture in exhaust gas. Thus, a high degree of denitrationcan be achieved even at high humidity. Moreover, only oxidizingoxygen-containing functional groups such as C═O can be introduced byheat-treating the raw active carbon in a non-oxidizing atmosphere andthen activating it with sulfuric acid or nitric acid. Thus, a highdegree of denitration can be achieved even at low temperatures rangingfrom ordinary temperature to about 150° C., without any reduction inadsorption performance.

EXAMPLES

The features of the present invention are more clearly is explained withreference to the following examples and comparative examples. However,these examples are not to be construed to limit the scope of the presentinvention.

Examples 1-9

Heat-treated active carbon fibers in accordance with the presentinvention were produced by heat-treating the following three types ofpitch-derived raw active carbon fibers (all manufactured by Osaka GasCo., Ltd.) at 600-1,200° C. in an atmosphere of nitrogen for one hour.

OG-5A; specific surface area, 500 m²/g

OG-10A; specific surface area, 1,000 m²/g

OG-20A; specific surface area, 2,000 m²/g

2 g each of the heat-treated active carbon fibers obtained as above wereseparately packed in tubular reactors (25 mm in inner diameter), and anitrogen oxide-containing gas was passed therethrough at a temperatureof 150° C. and a flow rate of 400 cc/min. The nitrogen oxide-containinggas was composed of 150 ppm NO, 150 ppm NH₃, 15% O₂ and the balance N₂,and its moisture content was 80% as expressed in terms of the partialpressure of water vapor.

The effluent gas from each reactor was analyzed with a chemoluminescencetype NO_(x) meter (ECL-88US; manufactured by Yanagimoto Seisakusho), andthe degree of denitration was calculated according to the followingequation.

Degree of denitration (%)=[Inlet NO concentration (ppm)−Outlet NOconcentration (ppm)]÷Inlet NO concentration (ppm)×100

The steady-state values obtained in a stabilized state 30 hours afterthe start of the reaction are shown in Table 1.

The atomic oxygen/carbon ratio at the surfaces of the active carbonfibers (hereinafter referred to as O/C) was measured with aphotoelectron spectroscopic analyzer (“ESCA850”; manufactured byShimadzu Corp.).

Comparative Examples 1-3

Instead of being heat-treated, the three types of pitch-derived rawactive carbon fibers used in Examples 1-9 were directly packed intubular reactors similar to those used in Examples 1-9, and subjected todenitration reaction in the same manner as in Examples 1-9. The resultsthus obtained are also shown in Table 1.

TABLE 1 Heat-treating Degree of Type of temperature denitration sample(° C.) (%) O/C Comparative OG-5A — 2 0.122 Example 1 Example 1 OG-5A 60020 0.047 Example 2 OG-5A 800 33 0.033 Example 3 OG-5A 1,000 26 0.025Comparative OG-10A — 3 0.096 Example 2 Example 4 OG-10A 600 22 0.050Example 5 OG-10A 800 28 0.044 Example 6 OG-10A 1,000 25 0.023Comparative OG-20A — 2 0.080 Example 3 Example 7 OG-20A 600 18 0.045Example 8 OG-20A 800 24 0.035 Example 9 OG-20A 1,000 20 0.025

It is evident from the results shown in Table 1 that the heat-treatedactive carbon fibers exhibit an excellent denitrating effect.

Examples 10-18

The same three types of pitch-derived raw active carbon fibers as usedin Examples 1-9 were heat-treated at 600-1,200° C. in an atmosphere ofnitrogen for one hour, and then activated by adding sulfuric acid (98%)to the carbon fibers in an amount equal to three times the weight of thecarbon fibers, soaking them fully in the sulfuric acid, and heating themat 400° C. until the sulfuric acid was evaporated completely.

2 g each of the heat-treated carbon fibers obtained as above were packedin tubular reactors in the same manner as in Examples 1-9, and subjectedto denitration reaction in the same manner as in Examples 1-9. Theresults thus obtained are shown in Table 2.

TABLE 2 Heat- Activation treating with sulfuric Degree of Type oftemperature acid denitration sample (° C.) (° C.) (%) O/C Example 10OG-5A 600 400 40 0.054 Example 11 OG-5A 800 400 75 0.048 Example 12OG-5A 1,000 400 50 0.040 Example 13 OG-10A 600 400 32 0.055 Example 14OG-10A 800 400 55 0.048 Example 15 OG-10A 900 400 46 0.039 Example 16OG-20A 600 400 36 0.052 Example 17 OG-20A 800 400 48 0.040 Example 18OG-20A 900 400 40 0.036

It is evident from the results shown in Table 2 that the active carbonfibers modified by heat treatment and activation with sulfuric acidexhibit a more excellent denitrating effect.

Examples 19-43

Heat-treated active carbon fibers in accordance with the presentinvention were produced by heat-treating the following four types ofpitch-derived raw active carbon fibers (all manufactured by Osaka GasCo., Ltd.) at 600-1,200° C. in an atmosphere of nitrogen for one hour.

OG-7A: specific surface area, 700 m²/g

OG-8A; specific surface area, 800 m²/g

OG-10A; specific surface area, 1,000 m²/g

OG-20A; specific surface area, 2,000 m²/g

2 g each of the heat-treated active carbon fibers obtained as above wereseparately packed in tubular reactors (25 mm in inner diameter), and agas containing nitrogen oxide at a low concentration was passedtherethrough at a temperature of 25° C. and a flow rate of 400 cc/min.The nitrogen oxide-containing gas was composed of 10 ppm NO, 10 ppm NH₃,15% O₂ and the balance N₂, and its moisture content was 0% or 80% asexpressed in terms of relative humidity at 25° C.

The effluent gas from each reactor was analyzed with a chemoluminescencetype NO_(x) meter (ECL-88US; manufactured by Yanagimoto Seisakusho), andthe degree of denitration was calculated according to the followingequation.

Degree of denitration (%)=[Inlet NO concentration (ppm)−Outlet NOconcentration (ppm)]÷Inlet NO concentration (ppm)×100

The steady-state values obtained in a stabilized state 30 hours afterthe start of the reaction are shown in Tables 3 to 6.

The atomic oxygen/carbon ratio at the surfaces of the active carbonfibers was measured with a photoelectron spectroscopic analyzer(“ESCA850”; manufactured by Shimadzu Corp.).

Comparative Examples 4-11

Instead of being heat-treated, the four types of pitch-derived rawactive carbon fibers used in Examples 19-43 were directly packed intubular reactors similar to those used in Examples 19-43, and subjectedto denitration reaction in the same manner as in Examples 19-43. Theresults thus obtained are also shown in Tables 3 to 6.

TABLE 3 Heat-treating Degree of Surface Type of temperature denitrationoxygen/ sample (° C.) (%) carbon Relative humidity during reaction: 0%Comparative OG-7A — 60 0.122 Example 4 Example 19 OG-7A 600 65 0.047Example 20 OG-7A 700 66 0.042 Example 21 OG-7A 800 70 0.033 Example 22OG-7A 850 74 0.030 Relative humidity during reaction: 80% ComparativeOG-7A — 8 0.122 Example 5 Example 23 OG-7A 600 14 0.047 Example 24 OG-7A700 20 0.042 Example 25 OG-7A 800 30 0.033 Example 26 OG-7A 850 39 0.030

TABLE 4 Heat-treating Degree of Surface Type of temperature denitrationoxygen/ sample (° C.) (%) carbon Relative humidity during reaction: 0%Comparative OG-8A — 58 0.115 Example 6 Example 27 OG-8A 600 65 0.044Example 28 OG-8A 700 66 0.039 Example 29 OG-8A 800 72 0.030 Example 30OG-8A 855 75 0.027 Relative humidity during reaction: 80% ComparativeOG-8A — 22 0.115 Example 7 Example 31 OG-8A 600 30 0.044 Example 32OG-8A 700 33 0.029 Example 33 OG-8A 800 42 0.030 Example 34 OG-8A 850 460.027

TABLE 5 Heat-treating Degree of Surface Type of temperature denitrationoxygen/ sample (° C.) (%) carbon Relative humidity during reaction: 0%Comparative OG-10A — 48 0.096 Example 8 Example 35 OG-10A 600 64 0.050Example 36 OG-10A 850 42 0.043 Relative humidity during reaction: 80%Comparative OG-10A — 9 0.096 Example 9 Example 37 OG-10A 600 18 0.050Example 38 OG-10A 850 24 0.043 Example 39 OG-10A 900 20 0.035

TABLE 6 Heat-treating Degree of Surface Type of temperature denitrationoxygen/ sample (° C.) (%) carbon Relative humidity during reaction: 0%Comparative OG-20A — 42 0.080 Example 10 Example 40 OG-20A 600 50 0.045Example 41 OG-20A 850 38 0.035 Relative humidity during reaction: 80%Comparative OG-20A — 6 0.080 Example 11 Example 42 OG-20A 600 15 0.045Example 43 OG-20A 850 16 0.035

It is evident from the results shown in Tables 3 to 6 that the activecarbon fibers modified by heat treatment exhibit an excellentdenitrating effect.

Examples 44-47

One type of phenol-derived active carbon fibers [“FE-300” (trade name);manufactured by Toho Rayon Co., Ltd.; specific surface area, 850 m²/g]was heat-treated in the same manner as in Examples 19-43, and then usedto treat a NO-containing gas. The results thus obtained are shown inTable 7.

Comparative Examples 12-13

Instead of being heat-treated, the two types of phenol-derived rawactive carbon fibers used in Examples 44-47 were directly packed intubular reactors similar to those used in Examples 44-47, and subjectedto denitration reaction in the same manner as in Examples 44-47. Theresults thus obtained are also shown in Table 7.

TABLE 7 Heat-treating Degree of Surface Type of temperature denitrationoxygen/ sample (° C.) (%) carbon Relative humidity during reaction: 0%Comparative FE-300 — 64 0.250 Example 12 Example 44 FE-300 600 50 0.120Example 45 FE-300 850 40 0.050 Relative humidity during reaction: 80%Comparative FE-300 — 5 0.250 Example 13 Example 46 FE-300 600 14 0.120Example 47 FE-300 850 8 0.050

It is evident from the results shown in Table 7 that the heat-treatedactive carbon fibers derived from phenol exhibit an improved denitratingeffect, especially under high-humidity conditions including a relativehumidity of 80%.

Now, several embodiments of the denitration system in accordance withthe present invention are explained in greater detail. However, it is tobe understood that the present invention is not limited thereto.

FIRST EMBODIMENT OF THE DENITRATION SYSTEM

FIG. 2 illustrates a first embodiment of the denitration system forpracticing the present invention.

In FIG. 2, reference numerals 1 and 2 designate a first packed reactorand a second packed reactor, respectively.

As shown in this figure, the first and second packed reactors are packedwith a heat-treated active carbon which has been produced byheat-treating a raw active carbon at a temperature in the range of 600to 1,000° C.

A nitrogen oxide-containing gas to be treated, together with ammonia(NH₃), is introduced into first packed reactor 1 where nitrogen oxides(NO_(x)) present in the gas to be treated are brought into contact withthe ammonia and removed by the continuous selective reduction of them tonitrogen (N₂). Moreover, in second packed reactor 2, any excess ammoniaremaining after the reaction is recovered by adsorption.

As the heat-treated active carbon packed into the aforesaid first packedreactor 1 and second packed reactor 2, there is used one obtained bychemically treating pitch-derived carbon fibers (formed by the meltspinning of pitch obtained as residue in coal chemical and petrochemicalprocesses) under the following conditions.

In this embodiment, the aforesaid pitch-derived active carbon fiberscomprised pitch-derived active carbon fibers “OG-5A” (trade name)manufactured by Osaka Gas Co., Ltd. These active carbon fibers werefired at about 850° C. in a reducing atmosphere for one hour, shapedinto a corrugated form, and then used in the embodiment.

Moreover, when polyacrylonitrile (PAN)-derived active carbon fibersobtained by firing and carbonizing high-molecular-weightpolyacrylonitrile fibers [“FE-300” (trade name); manufactured by TohoRayon Co., Ltd.] were used as the heat-treated active carbon, theconcentration of nitrogen oxides (NO_(x)) in exhaust gas could also bereduced in the same manner as described above.

Furthermore, when a granular active carbon [“HC-30” (trade name);manufactured by Tsurumi Coal Co., Ltd.] heat-treated at 400-1,400° C. inan atmosphere of nitrogen for one hour was used as the heat-treatedactive carbon, the concentration of nitrogen oxides (NO_(x)) in exhaustgas could also be reduced in the same manner as described above.

Besides the aforesaid heat treatment, the denitration performance andammonia adsorption performance of active carbon can be improved bysubjecting it to any of the following chemical treatments.

Sulfuric Acid Treatment

This treatment comprises adding a raw active carbon to a mixturecomposed of 100 parts by weight of active carbon, 300 parts by weight ofsulfuric acid, and 200 parts by weight of water, heating the resultingmixture at 60-70° C. to evaporate the water, and holding it at 400° C.(or 300-1,200° C.) in an inert gas (N₂) for 4 hours.

Metal Carrying Treatment

This treatment comprises adding a raw active carbon to a mixturecomposed of 100 parts by weight of active carbon, 10 parts by weight ofiron nitrate, and 300 parts by weight of water, heating the resultingmixture at 60-70° C. to evaporate the water, and holding it at 400° C.(or 300-1,200° C.) in an inert gas (N₂) for 4 hours.

Copper nitrate, manganese nitrate, nickel nitrate, cobalt nitrate, zincnitrate and the like may also be used in place of the aforesaid ironnitrate.

The active carbon which has been subjected to a chemical treatment suchas the aforesaid sulfuric acid treatment or metal carrying treatmentshows an improvement not only in denitration performance but also inammonia adsorption performance, and can hence be applied to thedenitration system in place of the aforesaid heat-treated active carbon.The active carbon which has been subjected to such a chemical treatmentcan also be used in other embodiments which will be described later.

SECOND EMBODIMENT OF THE DENITRATION SYSTEM

FIG. 3 illustrates a second embodiment of the denitration system inaccordance with the present invention.

In FIG. 3, reference numeral 11 designates a first packed reactor; 12, asecond packed reactor; 13 to 18, valves; and 19, an ammonia supply line.

As shown in FIG. 3, this denitration system is constructed so that a gasto be treated is alternately introduced into a first packed reactor 11and a second packed reactor 12 which are packed with a heat-treatedactive carbon produced by heat-treating a raw active carbon at atemperature in the range of 600 to 1,000° C., whereby the gas issubjected to denitration reaction and any excess ammonia is recovered byadsorption.

In the first-step operation of this embodiment, as shown in FIG. 3(A),valves 13-15 are opened, valves 16-18 are closed, and an excess ofammonia (NH₃) is introduced through an ammonia supply line 19. Thus, infirst packed reactor 11, nitrogen oxides (NO_(x)) present in the gas tobe treated are brought into contact with the ammonia introduced togetherwith the gas, and removed by the continuous selective reduction of themto nitrogen (N₂).

The gas from which nitrogen oxides have been removed is passed throughvalve 14 and introduced into second packed reactor 12 which is packedwith the aforesaid heat-treated active carbon, where any excess ammoniais recovered by adsorption.

In the succeeding second-step operation, as shown in FIG. 3(B), valves13-15 are closed, valves 16-18 are opened, and an excess of ammonia(NH₃) is introduced through ammonia supply line 19. Thus, in secondpacked reactor 12, nitrogen oxides (NO_(x)) present in the gas to betreated are brought into contact with the ammonia introduced togetherwith the gas, and removed by the continuous selective reduction of themto nitrogen (N₂).

During this process, the excess ammonia adsorbed in second packedreactor 12 during the aforesaid first-step operation is also used forpurposes of reduction, so that second packed reactor 12 is regenerated.

The gas from which nitrogen oxides have been removed is passed throughvalve 17 and introduced into first packed reactor 11, where any excessammonia is recovered by adsorption.

Thus, nitrogen oxides can be continuously and efficiently treated byintroducing a gas to be treated alternately into first packed reactor 11and second packed reactor 12 so as to perform denitration and ammoniaadsorption repeatedly.

THIRD EMBODIMENT OF THE DENITRATION SYSTEM

FIGS. 4 to 6 illustrate a third embodiment of the denitration system inaccordance with the present invention.

In FIGS. 4 to 6, reference numeral 21 designates a first ammoniaadsorber; 22, a second ammonia adsorber; 23, a denitrator; 24, anammonia supply source; and 25 to 30, valves.

As shown in FIGS. 4 to 6, this denitration system includes a firstammonia adsorber 21 and a second ammonia adsorber 22 which are packedwith a heat-treated active carbon produced by heat-treating a raw activecarbon at a temperature in the range of 600 to 1,000° C., and adenitrator 23 located therebetween and packed with a heat-treated activecarbon produced by heat-treating a raw active carbon at a temperature inthe range of 600 to 1,000° C. Exhaust gas is alternately introduced fromthe sides of first ammonia adsorber 21 and second ammonia adsorber 22,whereby the gas is subjected to denitration reaction and any excessammonia is recovered by adsorption.

In the first-step operation of this embodiment, as shown in FIG. 4,valves 25, 28 and 30 are opened, valves 26, 27 and 29 are closed, and anexcess of ammonia (NH₃) is introduced from an ammonia supply source 24into denitrator 23 by way of valve 28. Thus, in denitrator 23, nitrogenoxides (NO_(x)) present in the exhaust gas are brought into contact withthe ammonia introduced together with the exhaust gas, and removed by thecontinuous selective reduction of them to nitrogen (N₂).

The exhaust gas from which nitrogen oxides have been removed isintroduced into second ammonia adsorber 22 located on the downstreamside, where any excess ammonia is recovered by adsorption. Thereafter,the cleaned gas is discharged through valve 30.

In the succeeding second-step operation, as shown in FIG. 5, valves 25,28 and 30 are closed, valves 26, 27 and 29 are opened, and an excess ofammonia (NH₃) is introduced from ammonia supply source 24 intodenitrator 23 by way of valve 29. Thus, in denitrator 23, nitrogenoxides (NO_(x)) present in the gas to be treated are brought intocontact with the ammonia introduced together with the gas, and removedby the continuous selective reduction of them to nitrogen (N₂).

During this process, the excess ammonia adsorbed in second ammoniaadsorber 22 during the aforesaid first-step operation is also used forpurposes of reduction, so that second ammonia adsorber 22 isregenerated.

The exhaust gas from which nitrogen oxides have been removed isintroduced into first ammonia adsorber 21 located on the downstreamside, where any excess ammonia is recovered by adsorption. Thereafter,the cleaned gas is discharged through valve 27.

In the succeeding third-step operation, as shown in FIG. 6, valves 25,28 and 30 are opened, valves 26, 27 and 29 are closed, and an excess ofammonia (NH₃) is introduced from ammonia supply source 24 intodenitrator 23 by way of valve 28, similarly to the first-step operation.Thus, in denitrator 23, nitrogen oxides (NO_(x)) present in the gas tobe treated are brought into contact with the ammonia introduced togetherwith the gas, and removed by the continuous selective reduction of themto nitrogen (N₂).

During this process, the excess ammonia adsorbed in first ammoniaadsorber 21 during the aforesaid second-step operation is also used forpurposes of reduction, so that first ammonia adsorber 21 is regenerated.

The exhaust gas from which nitrogen oxides have been removed isintroduced into second ammonia adsorber 22 located on the downstreamside, where any excess ammonia is recovered by adsorption. Thereafter,the cleaned gas is discharged through valve 30.

Thus, nitrogen oxides can be continuously and efficiently treated byintroducing exhaust gas alternately into first ammonia adsorber 21 andsecond ammonia adsorber 22 so as to perform denitration and ammoniaadsorption repeatedly and, moreover, regenerate the ammonia adsorbers.

The treatment of exhaust gases discharged from boilers, gas turbines,engines and combustion furnaces for burning various types of fuel isfacilitated by applying the aforesaid denitration systems to the removalof nitrogen oxides (NO_(x)) present therein.

Moreover, the present invention can also be suitably used for theremoval of nitrogen oxides present in tunnels and for the removal ofnitrogen oxides present in exhaust gases from nitric acid productionplants.

1-20. (canceled)
 21. A denitration method comprising contacting a gascontaining one or more nitrogen oxides with a heat treated carbon,wherein said contacting results in reducing a concentration of thenitrogen oxides in the gas.
 22. The denitration method of claim 21,wherein the heat-treated carbon has an atomic surface oxygen/surfacecarbon ratio of 0.05 or less.
 23. The denitration method of claim 22,wherein the heat treated carbon is prepared by heat-treating an activecarbon at 600 to 1200° C. in a non-oxidizing atmosphere.
 24. Thedenitration method of claim 23, wherein a temperature of the gas is 100°C. or below.
 25. The denitration method of claim 21, wherein theheat-treated carbon was prepared by heat-treating an active carbon at600 to 1200° C. in a non-oxidizing atmosphere and activating a surfaceof the carbon with sulfuric or nitric acid.
 26. The denitration methodof claim 25, wherein a temperature of the gas ranges from 100° C. to150° C.
 27. The denitration method of claim 21, wherein one or morenitrogen oxides comprises NO.
 28. The denitration method of claim 21,wherein: a) prior to the contacting, the gas contains from about 20 to500 ppm of the one or more nitrogen oxides; b) a temperature of the gasis from 5° C. to about 150° C. during the contacting; and c) saidcontacting results in reducing the concentration of the nitrogen oxidesin the gas by about 40 to 80%.
 29. The denitration method of claim 21,wherein: a) prior to the contacting, the gas contains 15 ppm or less ofthe one or more nitrogen oxides; b) a temperature of the gas is from 5°C. up to about 150° C. during the contacting; and c) said contactingresults in reducing the concentration of the nitrogen oxides in the gasby about 40 to 80%.
 30. The denitration method of claim 29, wherein saidreducing is achieved without oxidizing NO to NO₂.
 31. The denitrationmethod of claim 29, wherein said reducing is achieved withoutconcentrating said nitrogen oxides.
 32. The denitration method of claim21, wherein the gas contains up to 80% of moisture as water vapor. 33.The denitration method of claim 21, wherein the gas contains greaterthan 80% of moisture as water vapor.
 34. The denitration method of claim21, wherein the heat treated carbon is prepared from an active carbonfiber derived from polyacrylonitrile or pitch.
 35. The denitrationmethod of claim 21, wherein said gas is an exhaust gas.
 36. Thedenitration method of claim 35, wherein said exhaust gas is an exhaustgas discharged from a boiler or an exhaust gas discharged from anexhaust gas denitration apparatus and wherein said contacting isperformed at an outlet of the boiler or at an outlet of the denitrationapparatus.
 37. The denitration method of claim 21, wherein said gas is aventilation gas produced in a road tunnel or an underground parkingspace.
 38. The denitration method of claim 21, wherein said gas has atemperature of 150° C. or below.
 39. The denitration method of claim 21,wherein said contacting results in decomposing the one or more nitrogenoxides into water and nitrogen.
 40. The denitration method of claim 21,wherein said contacting is performed in a presence of NH₃.